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Synthesis of structurally controlled hyperbranched polymers using a monomer having hierarchical reactivity.

ABSTRACT: Hyperbranched polymers (HBPs) have attracted significant attention because of their characteristic topological structure associated with their unique physical properties compared with those of the corresponding linear polymers. Dendrimers are the most structurally controlled HBPs, but the necessity of a stepwise synthesis significantly limits their applications in materials science. Several methods have been developed to synthesize HBPs by a one-step procedure, as exemplified by the use of AB2 monomers and AB' inimers under condensation and self-condensing vinyl polymerization conditions. However, none of these methods provides structurally controlled HBPs over the three-dimensional (3D) structure, i.e., molecular weight, dispersity, number of branching points, branching density, and chain-end functionalities, except under special conditions. Here, we introduce a monomer design concept involving two functional groups with hierarchical reactivity and demonstrate the controlled synthesis of dendritic HBPs over the 3D structure by the copolymerization of the designed monomer and acrylates under living radical polymerization conditions.

SUBMITTER: Lu Y

PROVIDER: S-EPMC5709361 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature

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Synthesis of structurally controlled hyperbranched polymers using a monomer having hierarchical reactivity.

Lu Yangtian Y Nemoto Takashi T Tosaka Masatoshi M Yamago Shigeru S

Nature communications 20171130 1

Hyperbranched polymers (HBPs) have attracted significant attention because of their characteristic topological structure associated with their unique physical properties compared with those of the corresponding linear polymers. Dendrimers are the most structurally controlled HBPs, but the necessity of a stepwise synthesis significantly limits their applications in materials science. Several methods have been developed to synthesize HBPs by a one-step procedure, as exemplified by the use of AB<su ...[more]

PMID: 29192274

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Project description:A new series of hyperbranched polymers consisting of fluorene-alt-carbazole as the branches and the three-dimensional-structured spiro[3.3]heptane-2,6-dispirofluorene (SDF) as the core were designed and synthesized by one-pot Suzuki coupling polycondensation. A phosphor group with broad full width at half maximum (FWHM) bis(1-phenyl-isoquinoline)(acetylacetonato)iridium(iii) (Ir(Brpiq)2acac, 0.08 mol%) as the red-light emitting unit and bis(2-(4-bromophenyl)-1-[6-(9-carbazolyl)hexyl]-imidazole)(2-(5-(4-fluorinated phenyl)-1,3,4-triazole)pyridine)iridium(iii) ((CzhBrPI)2Ir(fpptz)) as the green-light emitting unit were introduced into the backbones to obtain sunlight-style white-light emission by adjusting the feeding ratios of (CzhBrPI)2Ir(fpptz) (0.08 to 0.32 mol%). The results indicate the synthesized polymers show high thermal stabilities and good amorphous film morphology because of the hyperbranched structures. Besides, the lowest unoccupied molecular orbital (LUMO) levels of polymers were reduced and the electron injection was improved because of excellent electron-transporting ability of the triazole unit in the green group. The hyperbranched structures can effectively suppress the polymers' chain distortion and aggregation, and promote the incomplete Förster resonance energy transfer (FRET) efficiency from fluorene-alt-carbazole segments to Ir complex units. As a result, the devices with hyperbranched polymer light-emitting layers realize white light emission, and the optimized device also exhibits good electroluminescent (EL) performance with Commission Internationale de l'Eclairage (CIE) coordinates at (0.32, 0.31), a maximum luminance of 9054 cd m-2, a maximum current efficiency of 3.59 cd A-1 and a maximum Color Rendering Index (CRI) of 91. The hyperbranched polymers based on fluorene-alt-carbazole branches and a SDF core and high-efficiency phosphor groups with broad full width at half maximum are attractive candidates for sunlight-style white polymer light-emitting device.

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Synthesis of structurally controlled hyperbranched polymers using a monomer having hierarchical reactivity.

Publications

Synthesis of structurally controlled hyperbranched polymers using a monomer having hierarchical reactivity.

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